The cause of a large increase of atmospheric methane concentration during the Younger Dryas-Preboreal abrupt climatic transition (similar to 11,600 years ago) has been the subject of much debate. The carbon-14 (C-14) content of methane ((CH4)-C-14) should distinguish between wetland and clathrate contributions to this increase. We present measurements of (CH4)-C-14 in glacial ice, targeting this transition, performed by using ice samples obtained from an ablation site in west Greenland. Measured (CH4)-C-14 values were higher than predicted under any scenario. Sample (CH4)-C-14 appears to be elevated by direct cosmogenic C-14 production in ice. C-14 of CO was measured to better understand this process and correct the sample (CH4)-C-14. Corrected results suggest that wetland sources were likely responsible for the majority of the Younger Dryas-Preboreal CH4 rise.

Nitrogen and argon isotopes in air trapped in a Greenland ice core (GISP2) show two prominent peaks in the interval 11,800-10,800 B.P., which indicate two large abrupt warming events. The first abrupt wanning (10 +/- 4 degrees C) is the widely documented event at the end of the Younger Dryas. Here, we report on the second abrupt warming (4 +/- 1.5 degrees C), which occurred at the end of a short lived cooler interval known as the Preboreal Oscillation (11,270 +/- 30 B.P.). A rapid snow accumulation increase suggests that the climatic transition may have occurred within a few years. The character of the Preboreal Oscillation and the subsequent abrupt warming is similar to the Dansgaard-Oeschger (D/O) events in the last glacial period, suggestive of a common mechanism, but different from another large climate change at 8,200 B.P., in which cooling was abrupt but subsequent warming was gradual. The large abrupt warming at 11,270 B.P. may be considered to be the final D/O event prior to the arrival of the present stable and warm epoch. (c) 2008 Elsevier B.V. All rights reserved.

We present the first reconstruction of the Northern Hemisphere (NH) high latitude atmospheric carbon monoxide (CO) mole fraction from Greenland firn air. Firn air samples were collected at three deep ice core sites in Greenland (NGRIP in 2001, Summit in 2006 and NEEM in 2008). CO records from the three sites agree well with each other as well as with recent atmospheric measurements, indicating that CO is well preserved in the firn at these sites. CO atmospheric history was reconstructed back to the year 1950 from the measurements using a combination of two forward models of gas transport in firn and an inverse model. The reconstructed history suggests that Arctic CO in 1950 was 140-150 nmol mol(-1), which is higher than today's values. CO mole fractions rose by 10-15 nmol mol(-1) from 1950 to the 1970s and peaked in the 1970s or early 1980s, followed by a approximate to 30 nmol mol(-1) decline to today's levels. We compare the CO history with the atmospheric histories of methane, light hydrocarbons, molecular hydrogen, CO stable isotopes and hydroxyl radicals (OH), as well as with published CO emission inventories and results of a historical run from a chemistry-transport model. We find that the reconstructed Greenland CO history cannot be reconciled with available emission inventories unless unrealistically large changes in OH are assumed. We argue that the available CO emission inventories strongly underestimate historical NH emissions, and fail to capture the emission decline starting in the late 1970s, which was most likely due to reduced emissions from road transportation in North America and Europe.

New ice core analyses show that the prominent rise in atmospheric methane concentration at Dansgaard-Oeschger event 21 was interrupted by a century-long 20% decline, which was previously unrecognized. The reversal was found in a new similar to 100-year resolution study of methane in the GISP2 ice core, encompassing the beginning of D-O event 21, which also corresponds to the transition from MIS 5b to 5a. Although a corresponding reversal (within age uncertainty) is observed in climate proxies measured in GISP2 ice, including delta O-18(ice), electrical conductivity, light scattering, and several ions, this feature has not been discussed previously. Abrupt changes in methane are paralleled by changes in delta N-15 of trapped air, a quantity that reflects local temperature change at Greenland summit. The reversal described here supports the hypothesis that climate can be unstable during major transitions, as was previously described for the last deglaciation.

A new ice core from Siple Dome, Antarctica suggests the surface temperature increased by similar to6degreesC in just several decades at approximately 22 ka BP. This abrupt change did not occur 500 kin away in the Byrd ice core, or in climate proxy records in the Siple Dome core indicative of the mid-latitude Pacific. This demonstrates there was significant spatial heterogeneity in the response of the Antarctic climate during the last deglaciation and draws attention to unexplained mechanisms of abrupt climate change in Antarctica. (C) 2003 Elsevier Ltd. All rights reserved.

The last glacial period was terminated by an abrupt warming event in the North Atlantic similar to 15,000 years before the present, and warming events of similar age have been reported from Low Latitudes. Understanding the mechanism of this termination requires that the precise relative timing of abrupt climate warming in the tropics versus the North Atlantic be known. Nitrogen and argon isotopes in trapped air in Greenland ice show that the Greenland Summit warmed 9 +/- 3 degrees C over a period of several decades, beginning 14,672 years ago. Atmospheric methane concentrations rose abruptly over a similar to 50-year period and began their increase 20 to 30 years after the onset of the abrupt Greenland warming. These data suggest that tropical climate became warmer or wetter (or both) similar to 20 to 80 years after the onset of Greenland warming, supporting a North Atlantic rather than a tropical trigger for the climate event.

Argon and nitrogen isotopes of air in polar ice cores provide constraints on past temperature and firn thickness, with relevance to past climate. We developed a method to simultaneously measure nitrogen and argon isotopes in trapped air from the same sample of polar ice. This method reduces the time required for analysis, allowing large numbers of measurements. We applied this method to the entire Holocene sequence of the GISP2 ice core (82.37-1692.22 m) with a 10-20 year sampling interval (670 depths). delta(40)Ar and delta(15)N show elevated values in the oldest part of the dataset, consistent with a thicker firn layer and increased temperature gradient in the firn due to the legacy of the abrupt warming at the end of the Younger Dryas interval and the gradual warming during the Preboreal interval (11.5-10.0 ka). The Preboreal Oscillation and the 8.2k event are clearly recorded. The data show remarkable stability after the 8.2k event. Available data suggests that post-coring gas loss involves two distinct types of fractionation. First, smaller molecules with less than a certain threshold size leak through the ice lattice with little isotopic fractionation. Second, gas composition changes via gas loss through microcracks, which induces isotopic fractionation. These two gas loss processes can explain most trends in our data and in other ice core records. (C) 2008 Elsevier Ltd. All rights reserved.

Old ice for paleo-environmental studies, traditionally accessed through deep core drilling on domes and ridges on the large ice sheets, can also be retrieved at the surface from ice sheet margins and blue ice areas. The practically unlimited amount of ice available at these sites satisfies a need in the community for studies of trace components requiring large sample volumes. For margin sites to be useful as ancient ice archives, the ice stratigraphy needs to be understood and age models need to be established. We present measurements of trapped gases in ice from Taylor Glacier, Antarctica, to date the ice and assess the completeness of the stratigraphic section. Using delta O-18 of O-2 and methane concentrations, we unambiguously identify ice from the last glacial cycle, covering every climate interval from the early Holocene to the penultimate interglacial. A high-resolution transect reveals the last deglaciation and the Last Glacial Maximum (LGM) in detail. We observe large-scale deformation in the form of folding, but individual stratigraphic layers do not appear to have undergone irregular thinning. Rather, it appears that the entire LGM-deglaciation sequence has been transported from the interior of the ice sheet to the surface of Taylor Glacier relatively undisturbed. We present an age model that builds the foundation for gas studies on Taylor Glacier. A comparison with the Taylor Dome ice core confirms that the section we studied on Taylor Glacier is better suited for paleo-climate reconstructions of the LGM due to higher accumulation rates.

An understanding of the mechanisms that control CO2 change during glacial-interglacial cycles remains elusive. Here we help to constrain changing sources with a high-precision, high-resolution deglacial record of the stable isotopic composition of carbon in CO2 (delta C-13-CO2) in air extracted from ice samples from Taylor Glacier, Antarctica. During the initial rise in atmospheric CO2 from 17.6 to 15.5 ka, these data demarcate a decrease in delta C-13-CO2, likely due to a weakened oceanic biological pump. From 15.5 to 11.5 ka, the continued atmospheric CO2 rise of 40 ppm is associated with small changes in delta C-13-CO2, consistent with a nearly equal contribution from a further weakening of the biological pump and rising ocean temperature. These two trends, related to marine sources, are punctuated at 16.3 and 12.9 ka with abrupt, century-scale perturbations in delta C-13-CO2 that suggest rapid oxidation of organic land carbon or enhanced air-sea gas exchange in the Southern Ocean. Additional century-scale increases in atmospheric CO2 coincident with increases in atmospheric CH4 and Northern Hemisphere temperature at the onset of the Bolling (14.6-14.3 ka) and Holocene (11.6-11.4 ka) intervals are associated with small changes in delta C-13-CO2, suggesting a combination of sources that included rising surface ocean temperature.

Global climate and the concentration of atmospheric carbon dioxide (CO2) are correlated over recent glacial cycles(1,2). The combination of processes responsible for a rise in atmospheric CO2 at the last glacial termination(1,3) (23,000 to 9,000 years ago), however, remains uncertain(1-3). Establishing the timing and rate of CO2 changes in the past provides critical insight into the mechanisms that influence the carbon cycle and helps put present and future anthropogenic emissions in context. Here we present CO2 and methane (CH4) records of the last deglaciation from a new high-accumulation West Antarctic ice core with unprecedented temporal resolution and precise chronology. We show that although low-frequency CO2 variations parallel changes in Antarctic temperature, abrupt CO2 changes occur that have a clear relationship with abrupt climate changes in the Northern Hemisphere. A significant proportion of the direct radiative forcing associated with the rise in atmospheric CO2 occurred in three sudden steps, each of 10 to 15 parts per million. Every step took place in less than two centuries and was followed by no notable change in atmospheric CO2 for about 1,000 to 1,500 years. Slow, millennial-scale ventilation of Southern Ocean CO2-rich, deep-ocean water masses is thought to have been fundamental to the rise in atmospheric CO2 associated with the glacial termination(4), given the strong covariance of CO2 levels and Antarctic temperatures(5). Our data establish a contribution from an abrupt, centennial-scale mode of CO2 variability that is not directly related to Antarctic temperature. We suggest that processes operating on centennial timescales, probably involving the Atlantic meridional overturning circulation, seem to be influencing global carbon-cycle dynamics and are at present not widely considered in Earth system models.

We present a synchronization of the NGRIP, GRIP and GISP2 ice cores onto a master chronology extending back to 104 ka before present, providing a consistent chronological framework for these three Greenland records. The synchronization aligns distinct peaks in volcanic proxy records and other impurity records (chemo-stratigraphic matching) and assumes that these layers of elevated impurity content represent the same, instantaneous event in the past at all three sites. More than 900 marker horizons between the three cores have been identified and our matching is independently confirmed by 24 new and previously identified volcanic ash (tephra) tie-points. Using the reference horizons, we transfer the widely used Greenland ice-core chronology, GICC05modelext, to the two Summit cores, GRIP and GISP2. Furthermore, we provide gas chronologies for the Summit cores that are consistent with the GICC05modelext timescale by utilizing both existing and new gas data (CH4 concentration and delta N-15 of N-2). We infer that the accumulation contrast between the stadial and interstadial phases of the glacial period was -10% greater at Summit compared to at NGRIP. The delta O-18 temperature-proxy records from NGRIP, GRIP, and GISP2 are generally very similar and display synchronous behaviour at climate transitions. The 1180 differences between Summit and NGRIP, however, changed slowly over the Last Glacial Interglacial cycle and also underwent abrupt millennial-to-centennial-scale variations. We suggest that this observed latitudinal delta O-18 gradient in Greenland during the glacial period is the result of 1) relatively higher degree of precipitation with a Pacific signature at NGRIP, 2) increased summer bias in precipitation at Summit, and 3) enhanced Rayleigh distillation due to an increased source-to-site distance and a potentially larger source-to-site temperature gradient. We propose that these processes are governed by changes in the North American Ice Sheet (NAIS) volume and North Atlantic sea-ice extent and/or sea-surface temperatures (SST) on orbital timescales, and that changing sea-ice extent and SSTs are the driving mechanisms on shorter timescales. Finally, we observe that maxima in the Summit NGRIP delta O-18 difference are roughly coincident with prominent Heinrich events. This suggests that the climatic reorganization that takes place during stadials with Heinrich events, possibly driven by a southward expansion of sea ice and low SSTs in the North Atlantic, are recorded in the ice-core records. (C) 2014 Elsevier Ltd. All rights reserved.

Changes in atmospheric CO2 on millennial-to-centennial timescales are key components of past climate variability during the last glacial and deglacial periods (70-10 ka), yet the sources and mechanisms responsible for the CO2 fluctuations remain largely obscure. Here we report the C-13/C-12 ratio of atmospheric CO2 during a key interval of the last glacial period at submillennial resolution, with coeval histories of atmospheric CO2, CH4, and N2O concentrations. The carbon isotope data suggest that the millennial-scale CO2 variability in Marine Isotope Stage 3 is driven largely by changes in the organic carbon cycle, most likely by sequestration of respired carbon in the deep ocean. Centennial-scale CO2 variations, distinguished by carbon isotope signatures, are associated with both abrupt hydrological change in the tropics (e.g., Heinrich events) and rapid increases in Northern Hemisphere temperature (Dansgaard-Oeschger events). These events can be linked to modes of variability during the last deglaciation, thus suggesting that drivers of millennial and centennial CO2 variability during both periods are intimately linked to abrupt climate variability. Plain Language Summary Ice cores provide unique records of variations in atmospheric CO2 prior to the instrumental era. While it is clear that changes in atmospheric CO2 played a significant role in driving past climate change, it is unclear what in turn drove changes in atmospheric CO2. Here we investigate enigmatic changes in atmospheric CO2 levels during an interval of the last glacial period (similar to 50,000 to 35,000 years ago) that are associated with abrupt changes in polar climate. To determine the sources and sinks for atmospheric CO2, we measured the stable isotopes of carbon in CO2 and found that the primary source of carbon to the atmosphere was an organic carbon reservoir. Most likely, this carbon was sourced from a deep ocean reservoir that waxed and waned following changes in either the productivity of the surface ocean or stratification of the deep ocean. We also found that atmospheric CO2 can change on the centennial timescale during abrupt climate transitions in the Northern Hemisphere. This observation adds to a growing body of evidence that abrupt changes in atmospheric CO2 are an important component of past carbon cycle variability.

We sampled interstitial air from the perennial snowpack (firn) at a site near the West Antarctic Ice Sheet Divide (WAIS-D) and analyzed the air samples for a wide variety of gas species and their isotopes. We find limited convective influence (1.4-5.2 m, depending on detection method) in the shallow firn, gravitational enrichment of heavy species throughout the diffusive column in general agreement with theoretical expectations, a similar to 10 m thick lock-in zone beginning at similar to 67 m, and a total firn thickness consistent with predictions of Kaspers et al. (2004). Our modeling work shows that the air has an age spread (spectral width) of 4.8 yr for CO2 at the firn-ice transition. We also find that advection of firn air due to the 22 cm yr(-1) ice-equivalent accumulation rate has a minor impact on firn air composition, causing changes that are comparable to other modeling uncertainties and intrinsic sample variability. Furthermore, estimates of 1 age (the gas age/ice age difference) at WAIS-D appear to be largely unaffected by bubble closure above the lock-in zone. Within the lock-in zone, small gas species and their isotopes show evidence of size-dependent fractionation due to permeation through the ice lattice with a size threshold of 0.36 nm, as at other sites. We also see an unequivocal and unprecedented signal of oxygen isotope fractionation within the lock-in zone, which we interpret as the mass-dependent expression of a size-dependent fractionation process.

Air withdrawn from the firn, at four polar sites (Dome Fuji, H72 and YM85, Antarctica and North GRIP, Greenland) was measured for delta N-15 of N-2 and delta O-18 of O-2 to test for the presence of convective air mixing in the top part of the firn, known as the "convective zone". Understanding the convective zone and its possible relationship to surface conditions is important for constructing accurate ice-core greenhouse gas chronologies and their phasing with respect to climate change. The thickness of the convective zone was inferred from a regression line with barometric slope of the data in the deep firn. It is less than a few meters at H72 and NGRIP, whereas a substantial convective zone is found at Dome Fuji (8.6 +/- 2.6 m) and YM85 (14.0 +/- 1.8 m). By matching the outputs of a diffusion model to the data, effective eddy diffusivities required to mix the firn air are found. At the surface of Dome Fuji and YM85, these are found to be several times greater than the molecular diffusivity in free air. The crossover from dominance of convection to molecular diffusion takes place at 7 +/- 2, 11 +/- 2 and 0.5 +/- 0.5 m at Dome Fuji, YM85 and NGRIP, respectively. These depths can be used as an alternative definition of the convective zone thickness. The firn permeability at Dome Fuji is expected to be high because of intense firn metamorphism due to the low accumulation rate and large seasonal air temperature variation at the site. The firn layers in the top several meters are exposed to strong temperature gradients for several decades, leading to large firn grains and depth hoar that enhance permeability. The thick convective zone at YM85 is unexpected because the temperature, accumulation rate and near-surface density are comparable to NGRIP. The strong katabatic wind at YM85 is probably responsible for creating the deep convection. The largest convective zone found in this study is still only half of the current inconsistency implied from the deep ice core gas isotopes and firn densification models. (c) 2006 Elsevier B.V. All rights reserved.

Ice cores provide unique archives of past atmospheres and climate, but interpretation of trapped-gas records and their climatic significance has been hampered by a poor knowledge of the prevalence of air convection in the firn layer on top of polar ice sheets. In particular, the phasing of greenhouse gases and climate from ice cores has been obscured by a discrepancy between empirical and model-based estimates of the age difference between trapped gases and enclosing ice, which may be due to air convection. Here we show that deep air convection (>23 m) occurs at a windy, near-zero-accumulation rate site in central Antarctica known informally as the Megadunes site (80.77914 degrees S, 124.48796 degrees E). Deep convection is evident in depth profiles of air withdrawn from the firn layer, in the observed pattern of the nitrogen isotope ratio (15)N/(14)N, the argon isotope ratio (40)Ar/(36)Ar, and in the mixing ratios of the anthropogenic halocarbons methyl chloroform (CH(3)CCl(3)) and HFC-134a (CH(2)FCF(3)). Transport parameters (diffusivities) were inferred and air was dated using measured carbon dioxide (CO(2)) and methane (CH(4)) mixing ratios, by comparing with the Law Dome atmospheric record, which shows that these are the oldest firn air samples ever recovered (CO(2) mean age = 1863 AD). The low accumulation rate and the consequent intense metamorphism of the firn (due to prolonged exposure to seasonal temperature cycling) likely contribute to deep air convection via large grain size and vertical cracks that act as conduits for vigorous air motion. The Megadunes site provides a possible modern analog for the glacial conditions in the Vostok, Dome Fuji, and Dome C ice core records and a possible explanation for lower-than-expected (15)N/(14)N ratios in trapped air bubbles at these times. A general conclusion is that very low accumulation rate causes deep air convection via its effect on firn structural characteristics. (C) 2010 Elsevier B.V. All rights reserved.

The most recent glacial to interglacial transition constitutes a remarkable natural experiment for learning how Earth's climate responds to various forcings, including a rise in atmospheric CO2. This transition has left a direct thermal remnant in the polar ice sheets, where the exceptional purity and continual accumulation of ice permit analyses not possible in other settings. For Antarctica, the deglacial warming has previously been constrained only by the water isotopic composition in ice cores, without an absolute thermometric assessment of the isotopes' sensitivity to temperature. To overcome this limitation, we measured temperatures in a deep borehole and analyzed them together with ice-core data to reconstruct the surface temperature history of West Antarctica. The deglacial warming was 11.3 +/- 1.8 degrees C, approximately two to three times the global average, in agreement with theoretical expectations for Antarctic amplification of planetary temperature changes. Consistent with evidence from glacier retreat in Southern Hemisphere mountain ranges, the Antarctic warming was mostly completed by 15 kyBP, several millennia earlier than in the Northern Hemisphere. These results constrain the role of variable oceanic heat transport between hemispheres during deglaciation and quantitatively bound the direct influence of global climate forcings on Antarctic temperature. Although climate models perform well on average in this context, some recent syntheses of deglacial climate history have underestimated Antarctic warming and the models with lowest sensitivity can be discounted.

The thermal diffusion factor (alpha(T)) of Ar-40/Ar-36 in air has been measured in the laboratory for the first time. The mean values of alpha(T) x 10(3) that we find at -30.0 degreesC are 9.85 +/- 0.04 for air and 11.25 +/- 0.03 for pure argon. The latter value is more precise than the data found in the literature. The temperature dependence of the thermal diffusion factor in air in the range -60 to -10 degreesC can be described by an empirical equation alpha(T) x 10(3) = 26.08 - 3952/ (+/-1%), where is the effective average temperature. Results of this study are valuable for reconstruction of magnitudes of abrupt climate change events recorded in Greenland ice cores. For one abrupt warming event similar to15,000 years ago, near the end of the last glacial period, these results yield a warming of 11 +/- 3 degreesC over several decades or less. Theoretical calculations are not yet able to provide the needed accuracy, and the experimental results for the thermal diffusion factor in air should be used for paleoenvironmental studies.

Melt layers are clear indicators of extreme summer warmth on polar ice caps. The visual identification of refrozen meltwater as clear bubble-free layers cannot be used to study some past warm periods, because, in deeper ice, bubbles are lost to clathrate formation. We present here a reliable method to detect melt events, based on the analysis of Kr/Ar and Xe/Ar ratios in ice cores, and apply it to the detection of melt in clathrate ice from the Eemian at NEEM, Greenland. Additionally, melt layers in ice cores can compromise the integrity of the gas record by dissolving soluble gases, or by altering gas transport in the firn, which affects the gas chronology. We find that the easily visible 1 mm thick bubble-free layers in the WAIS Divide ice core do not contain sufficient melt to alter the gas composition in the core, and do not cause artifacts or discontinuities in the gas chronology. The presence of these layers during winter, and the absence of anomalies in soluble gases, suggests that these layers can be formed by processes other than refreezing of meltwater. Consequently, the absence of bubbles in thin crusts is not in itself proof of a melt event.

Commonly, three mechanisms of firn air transport are distinguished: molecular diffusion, advection, and near-surface convective mixing. Here we identify and describe a fourth mechanism, namely dispersion driven by synoptic-scale surface pressure variability (or barometric pumping). We use published gas chromatography experiments on firn samples to derive the along-flow dispersivity of firn, and combine this dispersivity with a dynamical air pressure propagation model forced by surface air pressure time series to estimate the magnitude of dispersive mixing in the firn. We show that dispersion dominates mixing within the firn lock-in zone. Trace gas concentrations measured in firn air samples from various polar sites confirm that dispersive mixing occurs. Including dispersive mixing in a firn air transport model suggests that our theoretical estimates have the correct order of magnitude, yet may overestimate the true dispersion. We further show that strong barometric pumping, such as at the Law Dome site, may reduce the gravitational enrichment of delta N-15-N-2 and other tracers below gravitational equilibrium, questioning the traditional definition of the lock-in depth as the depth where delta N-15 enrichment ceases. Last, we propose that Kr-86 excess may act as a proxy for past synoptic activity (or paleo-storminess) at the site.

Marine sediments, speleothems, paleo-lake elevations, and ice core methane and delta O-18 of O-2 (delta O-18(atm)) records provide ample evidence for repeated abrupt meridional shifts in tropical rainfall belts throughout the last glacial cycle. To improve understanding of the impact of abrupt events on the global terrestrial biosphere, we present composite records of delta O-18(atm) and inferred changes in fractionation by the global terrestrial biosphere (Delta epsilon(LAND)) from discrete gas measurements in the WAIS Divide (WD) and Siple Dome (SD) Antarctic ice cores. On the common WD timescale, it is evident that maxima in Delta epsilon(LAND) are synchronous with or shortly follow small-amplitude WD CH4 peaks that occur within Heinrich stadials 1, 2, 4, and 5 - periods of low atmospheric CH4 concentrations. These local CH4 maxima have been suggested as markers of abrupt climate responses to Heinrich events. Based on our analysis of the modern seasonal cycle of gross primary productivity (GPP)-weighted delta(OatmO)-O-18 of terrestrial precipitation (the source water for atmospheric O-2 production), we propose a simple mechanism by which Delta epsilon(LAND) tracks the centroid latitude of terrestrial oxygen production. As intense rainfall and oxygen production migrate northward, Delta epsilon(LAND) should decrease due to the underlying meridional gradient in rainfall delta O-18. A southward shift should increase Delta epsilon(LAND). Monsoon intensity also influences delta O-18 of precipitation, and although we cannot determine the relative contributions of the two mechanisms, both act in the same direction. Therefore, we suggest that abrupt increases in Delta epsilon(LAND) unambiguously imply a southward shift of tropical rainfall. The exact magnitude of this shift, however, remains under-constrained by Delta epsilon(LAND).